CN113292352A - Preparation method of unidirectional high-thermal-conductivity carbon/carbon composite material - Google Patents
Preparation method of unidirectional high-thermal-conductivity carbon/carbon composite material Download PDFInfo
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Abstract
A preparation method of a unidirectional high-thermal-conductivity carbon/carbon composite material belongs to the technical field of composite material preparation. The method comprises the steps of repeatedly hot-pressing, carbonizing, chemical vapor depositing, repeatedly high-pressure dipping high-carbon-residue asphalt, carbonizing and finally graphitizing the ultrahigh-modulus and high-heat-conductivity carbon fiber unidirectional cloth and asphalt powder to obtain the unidirectional high-heat-conductivity carbon/carbon composite material. The carbon/carbon composite material has extremely high thermal conductivity and bending strength along the axial direction of the carbon fiber with ultrahigh modulus and high thermal conductivity, and is suitable for heat dissipation of various tip equipment.
Description
Technical Field
The invention relates to a preparation method of a unidirectional high-thermal-conductivity carbon/carbon composite material, and belongs to the technical field of composite material preparation.
Background
Along with the rapid development of high-end science and technology equipment, the calorific capacity of components and parts is bigger and bigger, and its high-efficient heat dissipation has become the key problem that awaits solution urgently. Whether the materials are aerospace military equipment such as missile nosecones, airplane brake pads, rocket engine nozzle throat liners, aerospace airplane wing leading edges and nosecones and civil electrical appliance elements such as computers, 5G equipment and mobile communication equipment, a novel heat management material with light weight and high heat conductivity is urgently needed. The quality of the heat conducting performance of the material plays a key role in the performance of components.
The high-thermal-conductivity carbon/carbon composite material has a series of excellent performances such as high specific modulus, high specific strength, low density, thermal shock resistance, ablation resistance, high thermal conductivity, low expansion and the like, is one of the most potential and widely applied high-thermal-conductivity candidate materials at present, and the mechanical and thermal conductivity of the carbon/carbon composite material is closely related to the performances of raw materials, a preparation method and the like. From the current research situation at home and abroad, carbon fibers for preparing the high-thermal-conductivity carbon/carbon composite material mainly comprise pitch-based carbon fibers and vapor-grown carbon fibers. The carbon matrix is mainly pyrolytic carbon, pitch carbon, etc. The method for preparing the high-heat-conductivity carbon/carbon composite material by using the asphalt-based carbon fiber is different, the asphalt-based carbon fiber carbonized at about 1500 ℃ and having better flexibility is woven into carbon cloth in China, then the preparation process of the carbon/carbon plate is carried out, and finally the carbon cloth and the carbon/carbon plate are graphitized together at the high temperature of 2800-3000 ℃, so that the product quality is poor due to the high-temperature graphitization shrinkage of the carbon fiber, and how to directly use the graphite fiber with ultrahigh modulus and high heat conductivity for preparing the high-heat-conductivity carbon/carbon composite material through the processes of hot pressing, impregnation, vapor deposition, carbonization and the like is a problem needing to be researched and solved at present.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a method for preparing a unidirectional carbon/carbon composite material with high thermal conductivity, wherein the carbon/carbon composite material prepared by the method has extremely high thermal conductivity, and can meet the requirements of aerospace and electronic equipment on high thermal conductivity and light weight.
The preparation method of the unidirectional high-thermal-conductivity carbon/carbon composite material mainly comprises the following steps:
step (1), alternately laying ultrahigh-modulus and high-thermal-conductivity carbon fiber unidirectional cloth and asphalt powder in stainless steel molds with corresponding sizes, covering a mold cover plate, putting the mold cover plate on a hot press, performing hot-pressing composite molding under a certain temperature field and a certain pressure field, preserving heat and pressure for a period of time, and naturally cooling to obtain a prefabricated body;
step (2), carbonizing the prefabricated body without the die at high temperature, cooling and taking out the prefabricated body, then repeatedly spreading asphalt in a stainless steel die for hot pressing and carbonizing for 1-10 times to obtain a low-density carbon/carbon composite material, and finally enabling the asphalt in the low-density carbon/carbon composite material to completely bond the carbon fiber unidirectional cloth together and completely integrate the carbon fiber unidirectional cloth through the steps (1) and (2);
step (3), hydrocarbon gas is used as a carbon source, the low-density carbon/carbon composite material is subjected to deposition, permeation and pyrolysis carbon deposition at 800-2100 ℃ in a chemical vapor deposition mode to achieve the purposes of densification and reinforcement, the deposition time is 20-500 hours, a medium-density carbon/carbon composite material is obtained, and the hydrocarbon gas completely permeates and deposits into gaps of the low-density carbon/carbon composite material in the process until the weight or the density is not changed any more;
step (4), the carbon/carbon composite material with medium density is subjected to 1-15 times of repeated high-pressure impregnation, melting and carbonization of high-residual carbon asphalt to obtain a high-density carbon/carbon composite material; in the process, the molten high-carbon-residue asphalt continuously permeates and is filled into the carbon/carbon composite material with medium density until the weight or the density is not changed;
and (5) graphitizing the high-density carbon/carbon composite material at a high temperature of 2400-3000 ℃ for 0.1-30 h under an inert gas condition, and naturally cooling to obtain the unidirectional high-thermal-conductivity carbon/carbon composite material.
The ultrahigh-modulus and high-thermal-conductivity carbon fiber unidirectional cloth in the step (1) of the method is that the tensile modulus of a single carbon fiber is more than or equal to 500GPa, and the thermal conductivity is more than or equal to 400W/(m.K); the asphalt powder refers to coal asphalt or mesophase asphalt thereof, petroleum asphalt or mesophase asphalt thereof, naphthalene asphalt or mesophase asphalt thereof with ash content of less than 500ppm, and the softening point range of the asphalt powder is 60-320 ℃; the laying of the high-heat-conductivity carbon fiber unidirectional cloth is that the carbon fiber unidirectional cloth is laid in the same direction, the number of the laid layers is 1 or more, and the high-heat-conductivity carbon fiber unidirectional cloth can be freely adjusted according to actual needs.
The hot pressing process in the step (1) of the method has the specific conditions that: the hot pressing temperature is 10-100 ℃ higher than the softening point of the used asphalt, the hot pressing pressure is 0.1-15 MPa, and the heat preservation and pressure maintaining time is 0.1-10 h.
The hot pressing temperature and pressure in the step (2) of the method are the same as those in the step (1), and the carbonization temperature is 700-1600 ℃.
In the step (3), the hydrocarbon gas is a hydrocarbon gas such as methane, ethane, propane, ethylene, propylene, acetylene, etc., and the deposition is performed by a normal pressure gas flow.
In the step (4), the high-pressure impregnation is carried out under the pressure of 2-12 MPa; the high carbon residue asphalt refers to coal asphalt or mesophase asphalt thereof, petroleum asphalt or mesophase asphalt thereof, naphthalene asphalt or mesophase asphalt thereof, the carbon residue rate of which is more than or equal to 55 percent and the ash content of which is less than or equal to 500ppm, and the carbonization temperature is 700-1600 ℃.
The invention has the following advantages:
(1) the unidirectional high-thermal-conductivity carbon/carbon composite material has very high thermal conductivity and bending strength along the axial direction of the ultrahigh-modulus high-thermal-conductivity carbon fiber;
(2) the carbon fiber unidirectional cloth with ultrahigh modulus and high heat conductivity is directly used, so that the carbon/carbon composite material does not shrink any more in the subsequent graphitization process, and the high performance of the product is further ensured;
(3) the invention uses the technological processes of multiple times of hot pressing-carbonization, chemical vapor deposition, high-pressure impregnation-carbonization and the like, effectively improves the density of the prepared carbon/carbon composite material, and further increases the mechanical and heat-conducting properties of the carbon/carbon composite material;
drawings
Fig. 1 is a flow chart of the preparation process of the unidirectional high thermal conductive carbon/carbon composite material of the present invention.
Detailed Description
The present invention is illustrated by way of specific examples, but is not intended to be limited thereto.
Example 1:
alternately laying 5 layers of carbon fiber unidirectional cloth with the modulus of 600GPa and the thermal conductivity of 800W/(m.K) and coal tar pitch powder with the softening point of 158 ℃ and the ash content of 100ppm in stainless steel molds with corresponding sizes, covering a mold cover plate, putting the mold cover plate on a hot press, heating to 200 ℃, pressurizing to 5MPa, carrying out hot-pressing composite molding, keeping the temperature and the pressure for 0.5h, and naturally cooling to obtain a prefabricated body; carbonizing the prefabricated body without demoulding at 1000 ℃, cooling, taking out, and then repeatedly spreading asphalt in a stainless steel mould for hot pressing and carbonizing for 5 times to obtain the low-density carbon/carbon composite material with the thickness of 1 mm;
secondly, depositing, permeating and pyrolyzing carbon on the low-density carbon/carbon composite material at 1100 ℃ in a chemical vapor deposition mode by taking acetylene as a carbon source to achieve the purposes of densification and reinforcement, wherein the deposition time is 300h, and the medium-density carbon/carbon composite material is obtained; then, the carbon/carbon composite material with medium density is dipped into the molten coal-based mesophase pitch with the carbon residue rate of 70 percent under the pressure of 7MPa and carbonized (1200 ℃) for 8 times to obtain the carbon/carbon composite material with high density; finally, graphitizing the high-density carbon/carbon composite material at the high temperature of 2800 ℃ for 3h under the inert gas condition, naturally cooling to obtain the unidirectional high-heat-conductivity carbon/carbon composite material, wherein the thickness of the obtained unidirectional high-heat-conductivity carbon/carbon composite material is 1mm, and the density of the obtained unidirectional high-heat-conductivity carbon/carbon composite material is 1.81g/cm3The thermal conductivity is 652W/(m.K), and the bending strength is 217 MPa.
Example 2:
the using amount of the carbon fiber unidirectional cloth is increased from 5 layers to 6 layers, the other conditions are the same as the embodiment 1, the thickness of the obtained unidirectional high-heat-conductivity carbon/carbon composite material is 1mm, and the density is 1.80g/cm3The thermal conductivity coefficient is 672W/(m.K), and the bending strength is 247 MPa.
Example 3:
the carbon fiber unidirectional cloth with the modulus of 600GPa and the thermal conductivity of 800W/(m.K) is replaced by the carbon fiber unidirectional cloth with the modulus of 850GPa and the thermal conductivity of 800W/(m.K), other conditions are the same as those in the embodiment 1, and the obtained unidirectional high-thermal-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.73g/cm3The thermal conductivity is 647W/(m.K), and the bending strength is 223 MPa.
Example 4:
the carbon fiber unidirectional cloth with the modulus of 600GPa and the thermal conductivity of 800W/(m.K) is replaced by the carbon fiber unidirectional cloth with the modulus of 600GPa and the thermal conductivity of 1000W/(m.K), other conditions are the same as those in the embodiment 1, and the obtained unidirectional high-thermal-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.86g/cm3The thermal conductivity is 721W/(m.K), and the bending strength is 215 MPa.
Example 5:
replacing coal asphalt powder with softening point of 158 ℃ and ash content of 100ppm with petroleum asphalt powder with softening point of 137 ℃ and ash content of 100ppm, adjusting the corresponding hot pressing temperature to 180 ℃, and performing the other conditions in the same way as the embodiment 1 to obtain the unidirectional high-thermal-conductivity carbon/carbon composite material with the thickness of 1mm and the density of 1.75g/cm3The thermal conductivity is 635W/(m.K), and the bending strength is 228 MPa.
Example 6:
replacing coal pitch powder with softening point of 158 ℃ and ash content of 100ppm with coal-based mesophase pitch powder with softening point of 275 ℃ and ash content of 100ppm, correspondingly adjusting hot pressing temperature to 340 ℃, and performing the same other conditions as in the step 1 to obtain the unidirectional high-thermal-conductivity carbon/carbon composite material with the thickness of 1mm and the density of 1.94g/cm3The thermal conductivity coefficient is 676W/(mK), and the bending strength is 242 MPa.
Example 7:
the hot pressing pressure is increased from 5MPa to 6MPa, the other conditions are carried out in the same way as 1, and the obtained unidirectional high-thermal-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.98g/cm3The thermal conductivity is 662W/(m.K), and the bending strength is 240 MPa.
Example 8:
the heat preservation and pressure maintaining time of the hot press is increased from 0.5h to 1h, other conditions are carried out under the same condition 1, and the obtained unidirectional high-heat-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.82g/cm3The thermal conductivity is 657W/(m.K), and the bending strength is 223 MPa.
Example 9:
the carbonization temperature of the preform is reduced from 1000 ℃ to 900 ℃, the other conditions are the same as the embodiment 1, the thickness of the obtained unidirectional high-thermal-conductivity carbon/carbon composite material is 1mm, and the density is 1.63g/cm3Heat transferThe coefficient is 641W/(m.K), and the bending strength is 209 MPa.
Example 10:
increasing the number of times of repeated hot pressing from 5 times to 7 times, and performing the other conditions in the same way as 1 to obtain the unidirectional high-thermal-conductivity carbon/carbon composite material with the thickness of 1mm and the density of 1.95g/cm3The thermal conductivity was 658W/(m.K), and the bending strength was 222 MPa.
Example 11:
replacing a carbon source of chemical vapor deposition with acetylene into propylene under the same other conditions as in the step 1, wherein the thickness of the obtained unidirectional high-thermal-conductivity carbon/carbon composite material is 1mm, and the density of the unidirectional high-thermal-conductivity carbon/carbon composite material is 1.71g/cm3The thermal conductivity is 647W/(m.K), and the bending strength is 213 MPa.
Example 12:
reducing the chemical vapor deposition temperature from 1100 ℃ to 800 ℃, and carrying out the other conditions in the same way as the embodiment 1 to obtain the unidirectional high-thermal-conductivity carbon/carbon composite material with the thickness of 1mm and the density of 1.73g/cm3The heat conductivity coefficient is 598W/(m.K), and the bending strength is 204 MPa.
Example 13:
the chemical vapor deposition time is increased from 300h to 400h, other conditions are carried out in the same way as 1, and the obtained unidirectional high-thermal-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.95g/cm3The thermal conductivity coefficient is 672W/(m.K), and the bending strength is 236 MPa.
Example 14:
the times of high-pressure impregnation high-carbon-residue asphalt-carbonization are reduced from 8 times to 5 times, other conditions are carried out under the same condition 1, and the obtained unidirectional high-heat-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.77g/cm3The thermal conductivity is 637W/(m.K), and the bending strength is 198 MPa.
Example 15:
reducing the pressure of high-pressure impregnated high-carbon-residue asphalt from 7MPa to 3MPa, and carrying out the other conditions in the same way as the embodiment 1 to obtain the unidirectional high-heat-conductivity carbon/carbon composite material with the thickness of 1mm and the density of 1.67g/cm3The thermal conductivity is 626W/(m.K), and the bending strength is 200 MPa.
Example 16:
replacing molten coal-based mesophase pitch with carbon residue rate of 70%Forming molten petroleum-based mesophase pitch with a carbon residue rate of 75%, and performing the other conditions in the same way as in the step 1 to obtain the unidirectional high-thermal-conductivity carbon/carbon composite material with the thickness of 1mm and the density of 2.01g/cm3The thermal conductivity coefficient is 698W/(m.K), and the bending strength is 241 MPa.
Example 17:
the graphitization temperature is increased from 2800 ℃ to 3000 ℃, the other conditions are carried out 13, and the obtained unidirectional high-heat-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.90g/cm3The thermal conductivity is 703W/(m.K), and the bending strength is 238 MPa.
Example 18:
the graphitization time is increased from 3h to 5h, the other conditions are carried out in the same way as 13, and the obtained unidirectional high-heat-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.93g/cm3The thermal conductivity is 700W/(m.K), and the bending strength is 235 MPa.
Example 19:
the carbonization temperature of high-pressure impregnated high-carbon-residue asphalt-carbonization is increased from 1200 ℃ to 1500 ℃, other conditions are carried out in the same way as 1, and the obtained unidirectional high-heat-conductivity carbon/carbon composite material has the thickness of 1mm and the density of 1.75g/cm3The thermal conductivity is 645W/(m.K), and the bending strength is 204 MPa.
Example 20:
the using amount of the carbon fiber unidirectional cloth is increased from 5 layers to 10 layers, the unidirectional high-heat-conductivity carbon/carbon composite material with the thickness of 2mm is prepared under the same other conditions as the embodiment 1, the thickness of the obtained unidirectional high-heat-conductivity carbon/carbon composite material is 2mm, and the density is 1.87g/cm3The thermal conductivity coefficient is 661W/(m.K), and the bending strength is 310 MPa.
While the preferred embodiments of the present invention have been illustrated and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of a unidirectional high-thermal-conductivity carbon/carbon composite material is characterized by mainly comprising the following steps:
step (1), alternately laying ultrahigh-modulus and high-thermal-conductivity carbon fiber unidirectional cloth and asphalt powder in stainless steel molds with corresponding sizes, covering a mold cover plate, putting the mold cover plate on a hot press, performing hot-pressing composite molding under a certain temperature field and a certain pressure field, preserving heat and pressure for a period of time, and naturally cooling to obtain a prefabricated body;
step (2), carbonizing the prefabricated body without the die at high temperature, cooling and taking out the prefabricated body, then repeatedly spreading asphalt in a stainless steel die for hot pressing and carbonizing for 1-10 times to obtain a low-density carbon/carbon composite material, and finally enabling the asphalt in the low-density carbon/carbon composite material to completely bond the carbon fiber unidirectional cloth together and completely integrate the carbon fiber unidirectional cloth through the steps (1) and (2);
step (3), hydrocarbon gas is used as a carbon source, the low-density carbon/carbon composite material is subjected to deposition, permeation and pyrolysis carbon deposition at 800-2100 ℃ in a chemical vapor deposition mode to achieve the purposes of densification and reinforcement, the deposition time is 20-500 hours, a medium-density carbon/carbon composite material is obtained, and the hydrocarbon gas completely permeates and deposits into pores of the low-density carbon/carbon composite material in the process until the weight or the density is not changed any more;
step (4), the carbon/carbon composite material with medium density is subjected to 1-15 times of repeated high-pressure impregnation, melting and carbonization of high-residual carbon asphalt to obtain a high-density carbon/carbon composite material; in the process, the molten high-carbon-residue asphalt continuously permeates and is filled into the carbon/carbon composite material with medium density until the weight or the density is not changed;
and (5) graphitizing the high-density carbon/carbon composite material at a high temperature of 2400-3000 ℃ for 0.1-30 h under an inert gas condition, and naturally cooling to obtain the unidirectional high-thermal-conductivity carbon/carbon composite material.
2. The preparation method of the unidirectional carbon/carbon composite material with high thermal conductivity according to claim 1, wherein the ultrahigh-modulus and high-thermal-conductivity carbon fiber unidirectional cloth in the step (1) is a single carbon fiber with the tensile modulus of more than or equal to 500GPa and the thermal conductivity of more than or equal to 400W/(m.K); the asphalt powder refers to coal asphalt or mesophase asphalt thereof, petroleum asphalt or mesophase asphalt thereof, naphthalene asphalt or mesophase asphalt thereof with ash content of less than 500ppm, and the softening point range of the asphalt powder is 60-320 ℃; the laying of the high-heat-conductivity carbon fiber unidirectional cloth is that the carbon fiber unidirectional cloth is laid in the same direction, the number of the laid layers is 1 or more, and the high-heat-conductivity carbon fiber unidirectional cloth can be freely adjusted according to actual needs.
3. The preparation method of the unidirectional high thermal conductivity carbon/carbon composite material according to claim 1, wherein the hot pressing process in the step (1) is specifically carried out under the following conditions: the hot pressing temperature is 10-100 ℃ higher than the softening point of the used asphalt, the hot pressing pressure is 0.1-15 MPa, and the heat preservation and pressure maintaining time is 0.1-10 h.
4. The method for preparing a unidirectional carbon/carbon composite material with high thermal conductivity as claimed in claim 1, wherein the high temperature carbonization temperature of the preform in the step (2) is 700 to 1600 ℃.
5. The method for preparing a unidirectional carbon/carbon composite material with high thermal conductivity as claimed in claim 1, wherein the hydrocarbon gas in step (3) is a hydrocarbon gas such as methane, ethane, propane, ethylene, propylene, acetylene, etc., and the deposition is performed by an atmospheric pressure gas flow.
6. The preparation method of the unidirectional carbon/carbon composite material with high thermal conductivity as claimed in claim 1, wherein the high pressure impregnation in the step (4) is performed under a pressure of 2-12 MPa; the high carbon residue asphalt refers to coal asphalt or mesophase asphalt thereof, petroleum asphalt or mesophase asphalt thereof, naphthalene asphalt or mesophase asphalt thereof, the carbon residue rate of which is more than or equal to 55 percent and the ash content of which is less than or equal to 500ppm, and the carbonization temperature is 700-1600 ℃.
7. A unidirectional high thermal conductivity carbon/carbon composite prepared according to the process of any one of claims 1 to 6.
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